EP4336587A1 - Bleisäurebatterie-elektrodenplatte und verfahren zu ihrer herstellung sowie bleisäurebatterie - Google Patents

Bleisäurebatterie-elektrodenplatte und verfahren zu ihrer herstellung sowie bleisäurebatterie Download PDF

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Publication number
EP4336587A1
EP4336587A1 EP23181710.7A EP23181710A EP4336587A1 EP 4336587 A1 EP4336587 A1 EP 4336587A1 EP 23181710 A EP23181710 A EP 23181710A EP 4336587 A1 EP4336587 A1 EP 4336587A1
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EP
European Patent Office
Prior art keywords
electrode plate
lead
fiber
acid battery
air
Prior art date
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EP23181710.7A
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English (en)
French (fr)
Inventor
Shu-Huei Hsieh
Huai-Jen Wu
Chu-Ting Hsieh
Cun-Hao Xiao
You-Cheng Lin
Zhi-Xuan Yan
Jyun-Wei Lin
Chia-Yu Hsieh
Bo-jun LIU
Shang-Rong Li
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National Formosa University
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National Formosa University
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Publication of EP4336587A1 publication Critical patent/EP4336587A1/de
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H01M50/437—Glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/471—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof
    • H01M50/48—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to lead electrode plate structure and a method for making thereof, especially related to using non-metallic material to make an electrode plate for manufacturing a lead-acid battery.
  • the present invention also relates to an art for preventing lead-acid battery from lead (II) sulfate crystal growth piercing and enhancing the battery formation efficiency
  • the aqueous sulfuric acid solution immersing the electrode plate stack is prone to have chemical reaction with the electrode plate within the cassette.
  • the chemical reaction leads to that sulfuric acid concentration in central area of the electrode plate is lower than that in the surrounding area, which eventually results in issues of pure hydration in central area of the electrode plate.
  • Pure hydration in central area of the electrode plate makes it easier for lead sulfate to dissolve into the aqueous sulfuric acid, and crystalize on the electrode plate to grow lead dendrite.
  • the lead dendrites gradually bridge between the electrode plates and eventually cause short circuit of the battery.
  • Electrode plate stack prepared by stacking conventional electrode plates creates insufficient porosity for air permeability from one plate to another.
  • the electrode plate surface is covered by a lead paste paper so as to prevent lead paste coated upon the electrode plate from sticking to other battery components such as another electrode plate or a separator.
  • lead paste paper for continuous lead paste coating process could not provide sufficient air permeability.
  • lead-acid battery such as lead-acid battery having capacity above 50Ah or 100Ah
  • the size of their electrode plates are often larger than those in a conventional lead-acid battery.
  • Larger-sized electrode plates render it difficult for the aqueous sulfuric acid solution in central area of the electrode plate to reach an equilibrium in terms of concentration with the aqueous sulfuric acid solution in the surrounding area through convective diffusion.
  • pure hydration tends to be observed in central area of the larger-sized electrode plate such that lead sulfate is dissolved and attached to the lead paste paper or the separator.
  • the attached lead sulfate attracts more lead microparticles to grow into lead dendrite.
  • the continuously growing lead dendrite pierces through the separator and bridge between positive and negative electrode plates, causing battery short circuit.
  • the present invention discloses a lead-acid battery electrode plate for preventing lead sulfate dendrite growth and enhancing batter formation efficiency, comprising: a electricity collector layer provided to be an electricity channel; a first air-permeable layer comprising a non-metallic sheet material and provided on one side of the electricity collector layer; a second air-permeable layer comprising a non-metallic sheet material and provided on other side of the electricity collector layer in a corresponding manner to the first air-permeable layer, wherein the non-metallic sheet material has a porous structure to be air-permeable channels, and the first air-permeable layer is the same to or different from the second air-permeable layer.
  • the porous structure comprises one or more interwoven layers, and the interwoven layers are prepared by interweaving a plurality of latitudinal threads and a plurality of longitudinal threads, wherein an intersection angle formed between any one of the latitudinal threads intersecting with any one of the longitudinal threads is an acute angle or an obtuse angle.
  • the porous structure comprises an electrical conductive material, a corrosion-resistant material or a combination thereof, wherein the electrical conductive material comprises one or more materials selected from a group consisting of electrical conductive polymers, nanocarbon, graphite and graphene; the corrosion-resistant material comprises one or more materials selected from a group consisting of polypropylene fiber, polyethylene fiber, polyester fiber, nylon fiber, aramid fiber, polyvinyl chloride fiber, acrylic fiber, viscose fiber, glass fiber, spandex fiber, carbon fiber, polyacrylate fiber and polyimide fiber.
  • the electrical conductive material comprises one or more materials selected from a group consisting of electrical conductive polymers, nanocarbon, graphite and graphene
  • the corrosion-resistant material comprises one or more materials selected from a group consisting of polypropylene fiber, polyethylene fiber, polyester fiber, nylon fiber, aramid fiber, polyvinyl chloride fiber, acrylic fiber, viscose fiber, glass fiber, spandex fiber, carbon fiber, polyacrylate fiber and polyimide fiber.
  • the porous structure is a fabric braid comprising a fabric braid woven from long electrical conductive fiber materials, a fabric braid woven from long electrical conductive fiber materials and short electrical conductive fiber materials, a fabric braid woven from long corrosion-resistant fiber materials, a fabric braid woven from long corrosion-resistant fiber materials and short corrosion-resistant fiber materials, a fabric braid woven from long electrical conductive fiber materials and long corrosion-resistant fiber materials, or a fabric braid woven from long corrosion-resistant fiber materials, short corrosion-resistant fiber materials, and long corrosion-resistant fiber materials, short corrosion-resistant fiber materials.
  • the porous structure comprises a electrical conductive materials, a corrosion-resistant material or a combination thereof, wherein the electrical conductive materials is selected from a group consisting of electrical conductive polymers, nanocarbon, graphite and graphene; the corrosion-resistant material is glass fiber.
  • the present invention discloses a lead-acid battery comprising: a seal case; an electrode plate stack, sealed in the seal case, comprising: a separator; a positive electrode plate comprising the aforementioned lead-acid battery electrode plate, provided on one side of the separator; a negative electrode plate comprising the aforementioned lead-acid battery electrode plate, provided on the other side of the separator in a corresponding manner to the positive electrode plate; and an electrolyte solution, sealed in the seal case and immersing the electrode plate stack, dissolving acidic electrolyte.
  • the present invention discloses a method for making an lead-acid battery electrode plate comprising: placing one first non-metallic sheet material and one second non-metallic sheet material on two sides of the electricity collector layer in a respective manner so as to obtain the lead-acid battery electrode plate, wherein the first non-metallic sheet material and the second non-metallic sheet material have porous structures to be air-permeable channels of a first air-permeable layer and a second air-permeable layer, and the first air-permeable layer is the same as or different from the second air-permeable layer.
  • the porous structure comprises one or more interwoven layers
  • the interwoven layers are made by interweaving a plurality of latitudinal threads and a plurality of longitudinal threads, wherein an intersection angle formed between any one of the latitudinal threads intersecting with any one of the longitudinal threads is an acute angle or an obtuse angle.
  • the method further comprising exerting a pressure on the lead-acid battery electrode plate so as to laminate the electricity collector layer, the first non-metallic sheet material and the second non-metallic sheet material in a more intense manner.
  • the method comprises using a roller to exert the pressure on the first non-metallic sheet material-the electricity collector layer-the second non-metallic sheet material composite so as to obtain the lead-acid battery electrode plate.
  • the porous structure comprises a electrical conductive materials, a corrosion-resistant material or a combination thereof
  • the electrical conductive materials comprises one or more materials selected from a group consisting of electrical conductive polymers, nanocarbon, graphite and graphene
  • the corrosion-resistant material comprises one or more materials selected from a group consisting of polypropylene fiber, polyethylene fiber, polyester fiber, nylon fiber, aramid fiber, polyvinyl chloride fiber, acrylic fiber, viscose fiber, glass fiber, spandex fiber, carbon fiber, polyacrylate fiber and polyimide fiber.
  • he porous structure comprises a electrical conductive materials, a corrosion-resistant material or a combination thereof, wherein the electrical conductive materials is selected from a group consisting of electrical conductive polymers, nanocarbon, graphite and graphene; the corrosion-resistant material is glass fiber.
  • the present invention discloses a lead-acid battery comprising: a seal case; an electrode plate stack, sealed in the seal case, comprising: a separator; a positive electrode plate comprising a lead-acid battery electrode plate made by the aforementioned method, provided on one side of the separator; a negative electrode plate comprising a lead-acid battery electrode plate made by the aforementioned method, provided on the other side of the separator in a corresponding manner to the positive electrode plate; and an electrolyte solution, sealed in the seal case and immersing the electrode plate stack, dissolving acidic electrolyte.
  • the lead-acid electrode plate disclosed herein enhances air permeability of the lead-acid electrode plate itself. Gases which is produced during electrochemical reaction are more efficiently ventilated. Vulcanization on the lead-acid electrode plate is reduced so that short circuit of the battery due to lead dendrite growth is also suppressed. Meanwhile, electrical conductive materials are added to the non-metallic sheet materials, which benefits conductivity, electric capacity and formation efficiency. The corrosion-resistant materials ameliorates pure hydration issues in the central area of the electrode plate. Overall, the lead-acid battery can be more quickly put into subsequent applications, and battery lifespan is also significantly prolonged.
  • FIG. 1A illustrating a lead-acid battery electrode plate (100) provided in the present invention, comprising: a electricity collector layer (1) provided to be an electricity channel; a first air-permeable layer (2) comprising a non-metallic sheet material and provided on one side of the electricity collector layer; a second air-permeable layer (3) comprising a non-metallic sheet material and provided on other side of the electricity collector layer (1) in a corresponding manner to the first air-permeable layer (2), wherein the non-metallic sheet material has a porous structure to be air-permeable channels, and the first air-permeable layer (2) is the same to or different from the second air-permeable layer (3).
  • vulcanization tends to be observed in the surface of a lead-acid battery electrode plate, which results from electrochemical reaction between the electrolyte solution and the lead-acid battery electrode plate, and such a situation is hard to avoid.
  • Major reasons of surface vulcanization include large current discharge, deep discharge, not-timely charge, frequently charge or charge within overly short period.
  • enhancement of air permeability in the lead-acid electrode plate (100) not only increases ventilation of hydrogen and oxygen produced during charge and discharge, but also prevents battery damages caused by swelling pressure from the battery interiority.
  • surface vulcanization of the lead-acid battery electrode plate (100) can also be reduced, which suppresses lead dendrite growth that penetrates the adjacent separator.
  • the electricity collector layer (1) can be a lead grid (L) coated with lead paste (P) so as to increase electrical conductivity, electric capacity and charging performance of the lead-acid battery electrode plate (100).
  • the lead paste (P) comprises but not limited to lead powder, sodium lignosulfonate, short-fiber barium sulfate, and carbon materials such as carbon black or graphene.
  • the lead paste (P) can be prepared by mixing water, thin sulfuric acid and the materials as mentioned hereinabove.
  • the electricity collector layer (1) can be a unformed electrode plate, and any electrode plate that is not yet initiated by formation process can be the electricity collector layer (1), wherein the formation process is a well-known technique in the field of endeavor and will not be elaborated here.
  • the lead-acid battery electrode plate (100) is the negative plate (A) provided on one side of a positive plate (C), wherein at least one separator (S) is provided between the positive plate (C) and the negative plate (A).
  • the stacking of the electrode plates is similar to that of the electrode plate stack (1002), but the separator (S) wraps the positive plate (C) in a U shape, wherein the positive plate (C) can be the lead-acid battery electrode plate (100), or can be one lead-acid battery electrode plate made by any known craft.
  • the air-permeable layer facing the separator (S) requires higher air permeability.
  • the second air-permeable layer (3) having higher air permeability faces the separator (S), wherein the air permeability of the second air-permeable layer (3) is higher than the air permeability of the first air-permeable layer (2).
  • the air permeability is determined by averaged concentration of the electrolyte solution before and after the lead-acid battery electrode plate (100) is immersed in the electrolyte solution.
  • the porous structure is a fiber braid, comprising one or more interwoven layers.
  • the interwoven layers are prepared by interweaving a plurality of latitudinal threads and a plurality of longitudinal threads, wherein an intersection angle formed between any one of the latitudinal threads intersecting with any one of the longitudinal threads is an acute angle or an obtuse angle.
  • the acute angle measures between 0 to 90 degrees, but not 0 degree.
  • the obtuse angle measures between 90 to 180 degrees, but not 90 degrees or 180 degrees.
  • the latitudinal threads and the longitudinal threads can be long fibers, short fibers or any combination thereof. More preferably, a plurality of pores of various sizes are formed in the interwoven layers by random weaving the long fibers and the short fibers. The pores connects to each other and forms multiple air-permeable channels when the interwoven layers are stacked together to form the porous structure.
  • the air-permeable channels enhance the air permeability of the porous structure.
  • no crosslinking agent or binding agent is added because such additives would fill in the channels so that the air permeability is reduced.
  • thickness of the first air-permeable layer (2) ranges from 0.1 to 0.4 mm
  • thickness of the second air-permeable layer (3) ranges from 0.1 to 0.4 mm; preferably, thickness of the first air-permeable layer (2) ranges from 0.2 to 0.3 mm, and thickness of the second air-permeable layer (3) ranges from 0.2 to 0.3 mm.
  • the non-metallic sheet material is made of electrical conductive materials having high electrical conductivity.
  • the electrical conductive materials can be exemplified by electrical conductive polymers, activated carbon, nanocarbon, graphite or graphene.
  • the electrical conductive polymers can be polyacetylene-based polymers, polyparastyrene-based polymers, polyaniline, polypyrrol-based polymers, polyfluorene-based polymers, polyparaphenylene sulfide, polybenzazole-based polymers, polycarbazole-based polymers, polyazulene-based polymers, polynaphthyl polymers, polythiophene-based polymers, polythiophene-vinylidene polymers, or derivatives of any one thereof.
  • the electrical conductive materials are manufactured into electrical conductive fiber materials such as activated carbon fibers, nanocarbon fibers, graphite fibers or graphene fibers, and the interwoven layers are prepared by interweaving the electrical conductive fiber materials as the longitudinal threads and the latitudinal threads.
  • the electrical conductive materials are manufactured into electrical conductive cloth materials such as carbon fiber cloth, carbon nanotube fiber cloth, activated carbon cloth and graphene fiber cloth.
  • the "formation efficiency" is for evaluation of activation efficiency of a lead-acid battery in initial charge and discharge.
  • a passivated film is formed on the surface of either the positive electrode or the negative electrode, whereas the positive electrode having a thinner passivated film is not further discussed.
  • the passivated film is formed by consuming lead ions of the electrode plate when a chemical reaction is triggered between the electrolyte solution and the electrode plate. For example, lead sulfate is produced and forms a thin film blocking electrons and electrolyte solution. Formation efficiency is critical for lead-acid battery performance.
  • the lead-acid battery is charged using constant current and constant voltage methods, such as charging at rates of 0.1C, 0.2C or 0.3C, to evaluate whether the voltage consistency of lead-acid battery meets desired requirement during constant current charging.
  • the lead-acid battery produces gas in an electrochemical reaction. While at a particular voltage, a passivated film forms on the surface of negative electrode so that reductive reaction of the electrolyte solution is suppressed, and gas production also is decreased dramatically.
  • the non-metallic sheet material is made by interweaving non-electrical conductive corrosion-resistant materials and the electrical conductive materials.
  • the corrosion-resistant materials can be exemplified by polypropylene, polyethylene, polyester, nylon, aramid, polyvinyl chloride, acrylic, viscose, glass, spandex, polyacrylate, or polyimide; preferably, the corrosion-resistant materials are manufactured into corrosion-resistant fiber materials such as polypropylene fiber, polyethylene fiber, polyester fiber, nylon fiber, aramid fiber, polyvinyl chloride fiber, acrylic fiber, viscose fiber, glass fiber, spandex fiber, carbon fiber, polyacrylate fiber and polyimide fiber.
  • the corrosion-resistant fiber materials are subsequently interwoven as the longitudinal threads and the latitudinal threads into the interwoven layers, or the corrosion-resistant fiber materials and the electrical conductive fiber materials are taken as the longitudinal fibers and the latitudinal fibers, respectively, and interwoven into the interwoven layers, but not limited to this.
  • the porous structure is a fabric braid woven from long electrical conductive fiber materials ( Fig. 2A ), a fabric braid woven from long electrical conductive fiber materials and short electrical conductive fiber materials ( Fig. 2B ), a fabric braid woven from long corrosion-resistant fiber materials ( Fig. 2C ), a fabric braid woven from long corrosion-resistant fiber materials and short corrosion-resistant fiber materials ( Fig. 2D ), a fabric braid woven from long electrical conductive fiber materials and long corrosion-resistant fiber materials ( Fig. 2E ), or a fabric braid woven from long corrosion-resistant fiber materials, short corrosion-resistant fiber materials, and long corrosion-resistant fiber materials, short corrosion-resistant fiber materials ( Fig. 2F ), but not limited to this.
  • the non-metallic sheet material comprises 1.00 to 5.50wt% the electrical conductive materials and 0.10 to 2.00wt% the corrosion-resistant materials.
  • the non-metallic sheet material comprises 1.50 to 5.00wt% the electrical conductive materials and 0.20 to 1.50wt% the corrosion-resistant materials.
  • the non-metallic sheet material comprises 1.80 to 4.70wt% the electrical conductive materials and 0.25 to 1.25wt% the corrosion-resistant materials.
  • the present invention provides a lead-acid battery (200) comprising: a seal case (201); an electrode plate stack (202) sealed in the seal case (201), comprising: a separator (S); a positive electrode plate (C) comprising the lead-acid battery electrode plate (100), provided on one side of the separator (S); a negative electrode plate (A) comprising the lead-acid battery electrode plate (100), provided on the other side of the separator (S) in a corresponding manner to the positive electrode plate (C); and an electrolyte solution (E) sealed in the seal case and immersing the electrode plate stack (202).
  • a lead-acid battery comprising: a seal case (201); an electrode plate stack (202) sealed in the seal case (201), comprising: a separator (S); a positive electrode plate (C) comprising the lead-acid battery electrode plate (100), provided on one side of the separator (S); a negative electrode plate (A) comprising the lead-acid battery electrode plate (100), provided on the other side of
  • the electrolyte (E) is an aqueous acidic solution, generally an aqueous sulfuric acid solution, and a 30 to 40wt% aqueous sulfuric acid solution is preferred.
  • Fig. 3B illustrating another embodiment of the lead-acid battery (200), the components thereof are the same as described hereinabove, wherein another negative electrode plate (A') is provided on the other side of the positive electrode plate (C) corresponding to the negative electrode plate (A), and the another negative electrode plate (A') comprises the lead-acid battery electrode plate (100); another positive electrode plate (C') is provided on the other side of the another negative electrode plate (A') corresponding to the positive electrode plate (C), and the another positive electrode plate (C') comprises the lead-acid battery electrode plate (100); yet another negative electrode plate (A") is provided on the other side of the another positive electrode plate (C') corresponding to the another negative electrode plate (A'), and the yet another negative electrode plate (A") comprises the lead-acid battery electrode
  • any one of the positive electrode plates (C, C') is enclosed by the separators (S) so that the positive electrode (C, C') is isolated from the negative plate (A, A', A") adjacent the positive electrode (C, C').
  • the lead-acid battery (200) provided in the present invention demonstrates lower pure hydration in central area of the electrode plate than that of a conventional lead-acid battery during a manufacturing process.
  • the disparity in electrolyte concentration between central area and surrounding area of the lead-acid electrode plate (100) is smaller in comparison with that of a conventional lead-acid battery.
  • the "central area” is geometric center of the electrolyte-contacting surface of the electrode plate, and “surrounding area” is the outermost perimeter defining the electrode plate.
  • the shape of the electrode plate is not limited, and it can be a square, a round or any type of polygon, while the central area can be just defined in accordance to the definition of a polygonal geometric center in geometry.
  • the electrode plate is a rectangle, and the central area is the intersectional area of two diagonal lines, and the surrounding area is the area neighboring outer perimeter of the electrode plate.
  • the electrolyte (E) dissolves acidic electrolyte at a first concentration
  • the electrolyte (E) dissolves acidic electrolyte at a second concentration
  • the first concentration is lower than or equivalent to the second concentration, wherein a ratio of the first concentration to the second concentration is 1: (1 to 1.04); preferably, the ratio of the first concentration to the second concentration is 1: (1 to 1.03).
  • the separator (S) comprises a material selected from a group consisting of absorbent glass mat, polyvinyl chloride, polyolefin and non-woven fiber glass mat. In preferred embodiments, the separator (S) is made of absorbent glass mat.
  • Figs. 3D to 3E illustrating the gas ventilation of the lead-acid battery electrode plate (100) during charge and discharge, and the gas ventilation of the electrode plate in a conventional lead-acid battery, respectively.
  • the lead-acid battery electrode plate (100) can rapidly ventilate gas (G) produced in a charge-discharge reaction in that two air-permeable layers of non-metallic materials interwoven with fiber materials are provided, which provides ventilation channels between the separator (S) and the electricity collector layer (1). Heat accumulation is reduced and consumption of electrode plate is also minimized.
  • the electrode plate in a conventional lead-acid battery without the ventilation channels provided by interwoven fiber materials as shown in Fig.
  • the present invention provides a method for making an lead-acid battery electrode plate, as shown in Fig. 4A , comprising: Step S1: placing one first non-metallic sheet material (NM1) and one second non-metallic sheet material (NM2) on two sides of the electricity collector layer (1) in a respective manner so as to obtain the lead-acid battery electrode plate (100), wherein the first non-metallic sheet material (NM1) and the second non-metallic sheet material (NM2) have porous structures to be air-permeable channels of a first air-permeable layer (2) and a second air-permeable layer (3), and the first air-permeable layer (2) is the same as or different from the second air-permeable layer (3).
  • the method further comprises: Step S1-2: exerting a pressure on the lead-acid battery electrode plate (100) so as to laminate the electricity collector layer (1), the first non-metallic sheet material (NM1) and the second non-metallic sheet material (NM2) in a more compact manner, wherein the pressurizing procedure can be squeezing, rolling, or compressing by a compressor.
  • a raw electrode plate (RS) is roller-pressed through a roller system (300) to obtain an electrode plate strip (RSs), wherein the roller system (300) comprises a feeding device (31), a roller-pressing device (32) and a delivery device (33); the feeding device (31) feeds a lead grid (L) to a delivery belt (331), the first non-metallic sheet material (NM1) is fed from a first scroll (311) thereof to be placed between the delivery belt (331) and the lead grid (L) by the feeding device.
  • the roller system (300) comprises a feeding device (31), a roller-pressing device (32) and a delivery device (33); the feeding device (31) feeds a lead grid (L) to a delivery belt (331), the first non-metallic sheet material (NM1) is fed from a first scroll (311) thereof to be placed between the delivery belt (331) and the lead grid (L) by the feeding device.
  • a first rolling unit (321) is used to compactly press the lead grid (L) and the first non-metallic sheet material on the delivery belt (331) upon a first roller (332).
  • the second non-metallic sheet material (NM2) is fed from a second scroll (312) onto top side of the lead grid (L), and a second rolling unit (322) is used to compactly press, sequentially top to bottom, the second non-metallic sheet material (NM2), the lead grid (L) and the first non-metallic sheet material (NM1) on the delivery belt (331) upon a second roller (333).
  • the compacted electrode strip (RSs) is cut into the lead-acid battery electrode plate (100) according to needs.
  • the roller system (300) further comprises a material supplying device (34) for allocating a lead paste (P) to the lead grid (L).
  • the material supplying device (34) pours the lead paste (P) into each grid opening (O), and the lead paste (P) penetrates the lead grid (L) so as to envelope both sides of the lead grid (L).
  • the raw electrode plate (RS) comprises, sequentially top to bottom, the first non-metallic sheet material (NM1), the lead grid (L)-the lead paste (P), the second non-metallic sheet material (NM2), and compactly pressed by the second rolling unit (322) on the delivery belt (331) upon the second roller (333) so as to form the electrode plate strip (RSs).
  • the electrode plate strip (RSs) is cut into an individual lead-acid battery electrode plate (100), and dried, stored, and solidified so as for assembling a lead-acid battery.
  • the method further comprising:
  • an unformed electrode plate Preparing an unformed electrode plate sizing 23.9 cm in length, 16.2 cm in width, and 0.3 cm in thickness, and 2 pieces of non-metallic sheet materials having 2 cm thickness. Placing the unformed electrode plate between the 2 pieces of non-metallic sheet materials to obtain an electrode plate having air-permeable layers, wherein the non-metallic materials comprises carbon fibers and ceramic fibers.
  • Electrode plates in the embodiment 1 and the comparative example 1 were applied as the positive electrode plate (C) and the negative electrode plate (A).
  • the positive electrode plate (C) was enclosed by the separator (S), and alternatively stacked with the negative electrode plate (A) into an electrode plate stack.
  • the electrode plate stack was placed into a battery seal case to form a lead-acid battery.
  • the seal case was filled with aqueous sulfuric acid solution at concentration of 1.28M, and the electrode plate stack was immersed in the aqueous sulfuric acid solution for 40 minutes. Temperature of the aqueous sulfuric acid solution was measured around 40°C.
  • Probe of a densimeter reached the central area of the positive electrode plate (C) and the negative electrode plate (A), respectively, and reached surrounding area neighboring the electrode plate stack periphery fin order to measure concentrations of aqueous sulfuric acid solution. Pure hydration status could be determined through observing aqueous sulfuric acid concentration variations in central area of the electrode plate.
  • Fig. 5 illustrates the position where the concentration of aqueous sulfuric acid solution is measured, and the central area is the position where geometric center of the electrode plate lies at.
  • the concentration ratio of central area to surrounding area was lower (1.027 and 1.000, respectively) in comparison with the concentration ratio of central area to surrounding area (1.034 and 1.019, respectively) observed in comparative example 1.
  • the disparity in concentrations of the aqueous sulfuric acid solution between the central area and the surrounding area of the embodiment 1 was smaller. This demonstrates that the addition of non-metallic sheet materials to the embodiment 1 helped to more efficiently maintain the concentration of the aqueous sulfuric acid solution in central area of the electrode plate. This improvement addresses the pure hydration issues in central area of the electrode plate.
  • Electrode plates prepared in embodiment 1 and comparative example 1 were applied as positive electrode plates or negative electrode plates for assembling lead-acid batteries.
  • the lead-acid batteries were charged at a constant current of 0.17C and discharged at a constant current of 0.25C repeatedly for 3 times. Subsequently, surfaces of the electrode plates were observed whether there was lead sulfate dendrite growth or not.
  • FIG. 6A no surface lead sulfate dendrite growth was observed in electrode plate of the embodiment 1 after cyclic charge and discharge, and the separator remained in original color and not pierced through by any crystal dendrite.
  • FIG. 6B significant surface lead sulfate dendrite growth was observed in electrode plates of the comparative example 1, and the separator was penetrated by the lead sulfate dendrite, showing a deep-grey belt thereon.
  • the lead-acid electrode plate provided in the present invention demonstrates improvement of its air permeability by substituting conventional paste paper for the non-metallic sheet materials.
  • the lead-acid electrode plate could more efficiently ventilate gases produced in electrochemical reaction in comparison with the electrode plate using conventional paste paper. Therefore, electrolyte solution could move more rapidly from surrounding area to central area of the lead-acid electrode plate, and slows down concentration decrease in the central area.
  • Such improvement addresses pure hydration issues in central area of the lead-acid electrode plate. Meanwhile, battery damage owing to interior swelling pressure could be avoided. Surface vulcanization of the lead-acid battery can also be minimized to prevent battery short circuit resulting from lead dendrite.
  • the lead-acid electrode plate provided in the present invention exhibits superior characteristics compared to conventional paste paper. It not only enables efficient ventilation but also demonstrates excellent electrical conductivity and increased electric capacity. This is achieved by incorporating electrical conductive materials into the non-metallic sheet material. Along with increased electrical conductivity, formation efficiency of the lead-acid battery is also improved so that the lead-acid battery can be put into subsequent application more quickly. Furthermore, the incorporation of electrical conductive materials into the non-metallic sheet material helps reduce surface vulcanization. This reduction allows for the maintenance of a constant working area even after multiple cycles of charge and discharge. As a result, the battery exhibits improved long-term working efficiency with less decline over time, and the lifespan of the battery is also significantly prolonged.
  • Fibers of the non-metallic sheet materials are not interwoven in a perpendicular manner, which not only creates more channels for electrolyte solution flow, but also addresses pure hydration issues in central area of the lead-acid electrode plate by incorporation of the non-electrical conductive fiber materials to the electrical conductive fiber materials.
EP23181710.7A 2022-06-29 2023-06-27 Bleisäurebatterie-elektrodenplatte und verfahren zu ihrer herstellung sowie bleisäurebatterie Pending EP4336587A1 (de)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120244429A1 (en) * 2009-08-27 2012-09-27 Lan Trieu Lam Electrical storage device and electrode thereof
US20160372727A1 (en) * 2015-06-17 2016-12-22 Johns Manville Bi-functional nonwoven mat used in agm lead-acid batteries

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120244429A1 (en) * 2009-08-27 2012-09-27 Lan Trieu Lam Electrical storage device and electrode thereof
US20160372727A1 (en) * 2015-06-17 2016-12-22 Johns Manville Bi-functional nonwoven mat used in agm lead-acid batteries

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